US6406801B1 - Optical resonator type organic electroluminescent element - Google Patents

Optical resonator type organic electroluminescent element Download PDF

Info

Publication number
US6406801B1
US6406801B1 US09/243,479 US24347999A US6406801B1 US 6406801 B1 US6406801 B1 US 6406801B1 US 24347999 A US24347999 A US 24347999A US 6406801 B1 US6406801 B1 US 6406801B1
Authority
US
United States
Prior art keywords
transparent electrode
wavelength
mirror
organic layer
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US09/243,479
Inventor
Shizuo Tokito
Koji Noda
Hisayoshi Fujikawa
Yasunori Taga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Central R&D Labs Inc
Original Assignee
Toyota Central R&D Labs Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Central R&D Labs Inc filed Critical Toyota Central R&D Labs Inc
Assigned to KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO reassignment KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUJIKAWA, HISAYOSHI, NODA, KOJI, TAGA, YASUNORI, TOKITO, SHIZUO
Application granted granted Critical
Publication of US6406801B1 publication Critical patent/US6406801B1/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00Organic light-emitting devices
    • H10K50/80Constructional details
    • H10K50/85Arrangements for extracting light from the devices
    • H10K50/852Arrangements for extracting light from the devices comprising a resonant cavity structure, e.g. Bragg reflector pair
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/917Electroluminescent
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree

Definitions

  • the present invention relates to an optical resonator type organic electroluminescent element (hereafter referred to as the organic EL element), which is provided with a luminescent layer having an organic material held between a pair of electrodes, makes the luminescent layer emit light by injecting a carrier from both electrodes into the luminescent layer, and releases electromagnetic radiation in the form of light by resonating a specific wavelength in the emitted light.
  • the organic EL element optical resonator type organic electroluminescent element
  • the organic EL element has a luminescent layer of an organic material formed between an anode electrode and a cathode electrode, and electrons and electron holes, which are injected from the two electrodes into the luminescent layer, are recombined therein to generate light of a fluorescence spectrum corresponding to the organic material. This light is externally emitted as a natural emitted light without directivity from the organic EL element through a glass substrate.
  • an organic EL element having a minute optical resonator structure as shown in FIG. 1 .
  • the organic EL element having this resonator structure has an electron hole transportation layer 14 and a luminescent layer 16 of the organic material between an anode transparent electrode 12 and a cathode metallic electrode 50 , and it also has a multilayered film mirror 40 between a glass substrate 10 and the anode electrode 12 .
  • the minute optical resonance structure comprises the multilayered film mirror 40 and the metallic electrode 50 , and the light of a specific resonance wavelength, which is defined by a space between the multilayered film mirror 40 and the metallic electrode 50 , is amplified.
  • a luminescent material having a broad emission spectrum is used as the organic luminescent layer 16 , however, it is difficult to actually impart directivity to the luminescence light.
  • the directivity of light toward the front of the element can be improved by accurately controlling the space between the multilayered film mirror 40 and the metallic electrode 50 , as well as the position of a resonance wavelength, and also determining the optical length to a length of 1.5 times as long as a target wavelength ⁇ (JPA (Hei) 9-180883).
  • the above-mentioned organic EL element having an optical length of 1.5 ⁇ had an anode transparent electrode having a thickness of about 30 nm.
  • the transparent electrode is ITO (indium tin oxide) having a high electric conductivity, its sheet resistance is as high as 30 ⁇ / ⁇ , and it is impossible to prevent the generation of Joule heat.
  • ITO indium tin oxide
  • the transparent electrode is ITO (indium tin oxide) having a high electric conductivity, its sheet resistance is as high as 30 ⁇ / ⁇ , and it is impossible to prevent the generation of Joule heat.
  • the transparent electrode is ITO (indium tin oxide) having a high electric conductivity, its sheet resistance is as high as 30 ⁇ / ⁇ , and it is impossible to prevent the generation of Joule heat.
  • ITO indium tin oxide
  • the special luminescent material described in the above-mentioned document has a low luminous efficiency and unstable chemical performance. Therefore, it does not provide a highly effective element with high brightness.
  • the organic layer has a total film thickness of 100 nm or less, and the reliability of the element is low in view of a withstand voltage or the like due to a defect or the like, and the organic layer has high probability of a local short-circuit breakdown.
  • the above-described element is not realistic for practical use.
  • an optimum optical resonant organic EL element has not been provided yet, and there is not provided a resonant organic EL element which uses a luminescent material having high luminous efficiency and has high reliability at a large current. Besides, the satisfactory directivity of light toward the front of the element has not been achieved.
  • the present invention was achieved to solve the above-mentioned problems, and it is an object of the invention to improve the luminous efficiency and reliability of an organic EL element.
  • an organic electroluminescent element having a minute optical resonator for amplifying a specific wavelength in a luminescence light comprising a substrate; a multilayered film mirror formed of laminated layers on the substrate, each of the layers having a different refractive index; a transparent electrode as an anode on the multilayered film mirror; an organic layer on the transparent electrode; and a metallic electrode mirror as a cathode on the organic layer, said organic layer comprising a luminescent layer for emitting a light by injecting electron holes and electrons through the transparent electrode and the metallic electrode mirror, said multilayered film mirror and said metallic electrode mirror constituting a minute optical resonator for amplifying a specific wavelength in the light, wherein the minute optical resonator has an optical length twice as long as a target amplified wavelength, the organic layer is not less than 100 nm thick, and the transparent electrode is not less than 50 nm thick, or is of not more than 30 ⁇ in sheet resistance.
  • the “optical length” of the minute optical resonator is determined by a soaked quantity of light into the multilayered film mirror and an optical thickness of the organic layer (Document: J. Appl. Phys., 80 (1996) 6954).
  • the optical length is determined to be twice-as long as a target amplified wavelength ⁇ so to make it possible for the anode transparent electrode and the organic layer to have an appropriate thickness in view of the characteristics of the element.
  • the organic layer is characterized by determining the organic layer to have a thickness of 100 nm or more, and the transparent electrode to have a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 ⁇ / ⁇ or less.
  • the reliability of the organic layer is improved by determining its thickness to 100 nm or more.
  • Heat generation due to a large current flowing through the element can be suppressed by setting the transparent electrode to have a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 ⁇ / ⁇ or less.
  • the characteristics of the element can be prevented from being deteriorated due to heat generation, and the element can be driven at a large current and readily employed as a lighting device with high brightness.
  • the conditions described above are preferably determined so that a satisfactory emission intensity can be obtained, and light having high directivity can be emitted from the element.
  • the luminescent material with a narrow emission spectrum to configure the organic layer in order to additionally enhance the luminescence color purity of the organic EL element.
  • a luminescent material such as quinacridone having a half-width of about 80 nm or less.
  • FIG. 1 is a diagram showing the configuration of a general minute optical resonator type organic EL element
  • FIG. 2 is a diagram showing the configuration of the minute optical resonator type organic EL element according to Embodiment 1 of the present invention
  • FIG. 3 is a diagram showing brightness and current characteristics of the organic EL element of the invention compared with that of a conventional organic EL element for brightness and current characteristics;
  • FIGS. 4A and 4B are conceptual diagrams for illustrating differences of characteristics between the organic EL element of the invention and the conventional organic EL element due to the structural differences;
  • FIG. 5 is a diagram showing a positional relationship between the emission spectrum and the resonance wavelength of the luminescent layer of the minute optical resonator type organic EL element according to the embodiment of the invention.
  • FIG. 6 is a diagram showing the emission spectrum of the minute optical resonator type organic EL element when quinacridone is used as the luminescent layer;
  • FIG. 7 is a diagram showing the emission spectrum of the minute optical resonator type organic. EL element when alumiquinolinol complex is used as the luminescent layer;
  • FIG. 8 is a diagram showing an emission spectrum of the luminescent layer and its angle dependency
  • FIG. 9A is a diagram showing a position of the target amplified wavelength determined with respect to the peak wavelength of the emission spectrum of the luminescent layer
  • FIG. 9 B and FIG. 9C are diagrams illustrating characteristics of the emitted light obtained when the target amplified wavelength is determined as shown in FIG. 9A;
  • FIG. 10 A and FIG. 10B are diagrams illustrating an emission intensity and directivity of the emitted light obtained when the target amplified wavelength is determined to be on the side of a longer wavelength of the peak wavelength of the emission spectrum of the luminescent layer;
  • FIG. 11 is a diagram showing the configuration of the minute optical resonator type organic EL element according to an example of the invention.
  • FIG. 2 is a diagram showing the configuration of the minute optical resonator type organic EL element according to this embodiment-.
  • the organic EL element of this embodiment has a multilayered film mirror (dielectric mirror) 30 , which is formed by laminating two kinds of layers having a different refractive index into a plurality of layers, formed on a glass substrate 10 .
  • a transparent electrode 12 using ITO (indium tin oxide), SnO 2 , ln 2 O 3 or the like is formed as an anode on the multilayered film mirror 30 .
  • an organic layer which contains a luminescent layer 16 and an electron. hole transportation layer 14 , is formed on the transparent electrode 12 , and a metallic electrode mirror 20 is formed of Ag, MgAg, AlLi or Al with LiF as a cathode electrode on the organic layer.
  • a minute optical resonator comprises the multilayered film mirror 30 and the metallic electrode mirror 20 , and its optical length is a sum of a quantity of light soaked into the multilayered film mirror 30 and an optical thickness of the transparent electrode 12 and the organic layer.
  • the optical length is set to twice as long as a target amplified wavelength (resonance wavelength) ⁇
  • the transparent electrode 12 is determined to have a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 ⁇ / ⁇ or less.
  • the organic layer is determined to have a total thickness (the total thickness of the luminescent layer 16 and the electron hole transportation layer 14 ) 100 nm or more.
  • the sheet resistance becomes 30 ⁇ / ⁇ or more even if ITO is used as the transparent electrode when the optical length is 1.5 ⁇ and the transparent electrode has a thickness of about 30 nm as in the conventional art. Meanwhile, it is determined in this embodiment that the optical length is two times longer than the target amplified wavelength ⁇ , and the transparent electrode 12 has a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 ⁇ / ⁇ or less.
  • the transparent electrode 12 determines the transparent electrode 12 to have a thickness of ⁇ /2.
  • the transparent electrode 12 has a thickness of ⁇ /2 as above, its resistance can be decreased to half, and the Joule heat generated in the transparent electrode 12 using ITO can be decreased to 1 ⁇ 4 even by a simple calculation.
  • FIG. 3 shows the brightness and current characteristics of the element when the ITO transparent electrode as a thickness of ⁇ /4 or less as. in the conventional art and those of the element when ITO is used as the transparent electrode 12 and its thickness is ⁇ /2 as in the present embodiment.
  • a large current is caused to flow through the conventional element, it is deteriorated by the Joule heat to lower its brightness.
  • the element of this embodiment is hardly deteriorated by having a large current flow, and higher luminescence brightness is obtained with the increase of the amount of the current.
  • the element can be reliably prevented from having an increased temperature by increasing the thickness of the transparent electrode 12 so to have a very low sheet resistance, and stable light emission with high brightness can be carried out for a long time.
  • the entire organic layer is determined so as to have a thickness of 100 nm or more so that a local short-circuit breakdown in the organic EL element can be prevented, and the reliability of the element is secured.
  • FIG. 4 A and FIG. 4B conceptually show differences of actions between the resonator type organic EL element having an optical length of 1.5 ⁇ and the resonator type organic EL element having an optical length of 2 ⁇ as in this embodiment.
  • the element having the optical length of 1.5 ⁇ may have a high resistance because the transparent electrode 12 is thin, and since the organic layer is thin in addition, the transparent electrode 12 and the metallic electrode 50 might be partially short-circuited due to projections of the electrode layer or adhesion of dust or the like.
  • the conventional element has a short lifetime is that such a short-circuit is caused with a lapse of driving time.
  • FIG. 4A the element having the optical length of 1.5 ⁇ may have a high resistance because the transparent electrode 12 is thin, and since the organic layer is thin in addition, the transparent electrode 12 and the metallic electrode 50 might be partially short-circuited due to projections of the electrode layer or adhesion of dust or the like.
  • the element of this embodiment has an optical length of 2 ⁇ , and the transparent electrode 12 and the organic layer also have a sufficient thickness as described above. Therefore, it is unlikely that the electrodes are short-circuited due to the presence of dust or the projections of the electrode layer. In view of the reasons described above, the element of this embodiment can have a long service lifetime as described above.
  • the resonance wavelength of the third mode appears on the long wavelength side of the fourth mode.
  • the luminescent material has a small half-width of the emission spectrum (a width with which the maximum peak value becomes half).
  • the luminescent material to be used preferably has an emission spectrum not overlapping with 650 nm and a half-width of 80 nm or less.
  • the luminescent material satisfying the requirements described above contains quinacridone (half-width of 80 nm) expressed by the following chemical formula (1) for example.
  • FIG. 6 shows a relationship between a wavelength and an emission intensity (left vertical axis) under conditions that a target amplified wavelength is determined to 535 nm, the luminescent material containing the above-mentioned quinacridone is used as the luminescent layer, the organic layer has a thickness of 140 nm and the ITO electrode has a thickness of 150 nm.
  • FIG. 7 shows a relationship between a wavelength and an emission intensity (left vertical axis) under conditions that the target amplified wavelength is 500 nm, the luminescent layer is Alq, the organic layer has a thickness of 115 nm, the ITO electrode has a thickness of 150 nm, and an SiO 2 film and a Tio 2 film are each formed in four layers to configure the multilayered film mirror.
  • quinacridone has an emission spectrum of 650 nm or less and a half-width of 80 nm or less, and its spectrum does not overlap with the third peak generated in the neighborhood of 720 nm. Therefore, the emission spectrum of the resonant organic EL element finally obtained has its set wavelength in the neighborhood of 535 nm selectively amplified as indicated by broken chain line in FIG. 6 .
  • Alq alumiquinolinol complex
  • its emission spectrum has a large half-width and the spectrum also exists in the vicinity of 650 nm as indicated by a dotted line in FIG. 7 .
  • the resonance wavelength of the third mode has been m0 contained in this emission spectrum. Therefore, the optical resonant organic EL element using Alq as the luminescent layer also emits at the resonance wavelength of the third mode as indicated by broken chain line in FIG. 7 . Therefore, color purity is lowered, and the directivity toward the front of the element can not be obtained.
  • a red luminescent element in a low-level mode emits in an infrared region (700 nm or more)
  • a luminescent material with a large half-width can be used without involving any problem in a visual (for non-visual light for person).
  • perylene expressed by the chemical formula (3) an oxadiazol-based material expressed by the chemical formula (4), or distilarylene)-based material expressed by the chemical formula (5) can be used to emit blue light.
  • Phthalocyanine expressed by the chemical formula (6) or DCM2(5) expressed by the chemical formula (7) can be used to emit red light.
  • the electron hole transportation layer 14 which constitutes the organic layer with the luminescent layer 16 , is mainly composed of an aromatic amine-based material, such as TPTE (triphenylamine tetramer) expressed by the chemical formula (8) or ⁇ -NPB(Bis[N-(1-naphthyl)-N-phenyl] benzidine).
  • TPTE triphenylamine tetramer
  • the organic layer comprises the luminescent layer and the electron hole transportation layer.
  • an electron transportation layer using an organic material is formed between the luminescent layer and the metallic electrode mirror or an electron injection layer which consists of the oxide or fluoride of alkaline metal or alkaline-earth metal is formed therebetween.
  • the target amplified wavelength is determined to be about 30 nm toward the short wavelength side of the emitted peak wavelength of the luminescent layer as described above, and the reasons for doing so are given below.
  • the target amplified wavelength is determined to be at position ( ⁇ ) longer than 30 nm toward the shorter wavelength side from the luminescence peak, the directivity of the emitted light from the resonant organic EL element is very small as shown in FIG. 9 B.
  • the target amplified wavelength is determined on the longer wavelength side from the luminescence peak, such as position ( ⁇ ), as shown in FIG. 9A, the directivity is lost as shown in FIG. 9 C.
  • the target amplified wavelength is largely separated toward the long wavelength side from the luminescence peak, the emission spectrum itself of the luminescent layer in that region is small, so that the emitted light intensity itself at the front of the element also becomes small.
  • the directivity of the emitted light obtained by resonating becomes higher as the material for the luminescent layer has a steeper property on the short wavelength side of the luminescence peak.
  • this embodiment uses a luminescent material which has as steep a luminescence property as possible for the luminescent layer. Accordingly, the intensity of the emission spectrum of the luminescent layer itself is extremely small at a position more than 30 nm away toward the short wavelength side from the luminescence peak, and a satisfactory emission intensity cannot be obtained even if such a wavelength is determined as the target amplified wavelength. For example, in FIG.
  • quinacridone Qd has a luminescence peak wavelength of 540 nm, the short wavelength side 30 nm away from there is 510 nm, where the emission intensity of the original emission spectrum is only ⁇ fraction (1/30) ⁇ of the peak strength. Therefore, the target amplified wavelength is preferably determined to fall in a range of within 30 nm toward the short wavelength side from the luminescence peak wavelength.
  • FIGS. 10A and 10B specifically show the state described above.
  • FIG. 10A when the target amplified wavelength is determined on the long wavelength side of the luminescent layer and the observing direction is changed to shift the wavelength of the emitted light with the target amplified wavelength to the short wavelength side as described above, a region having a high emission intensity containing the luminescence peak of the original emission spectrum of the luminescent layer is on the short wavelength side of the shifted target amplified wavelength. Accordingly, as shown in FIGS.
  • the satisfactory emission intensity and directivity can be obtained by determining the target amplified wavelength to be within 30 nm on the short wavelength side of the luminescence peak of the luminescent layer.
  • FIG. 11 shows an example of the organic EL element of the present invention.
  • the multilayered film mirror was first formed on a cleaned glass substrate by alternately forming the SiO 2 film and the TiO 2 film each having a different refractive index (alternately four layers each to form eight layers in total) by a magnetron sputtering method.
  • a stop band optical reflected wavelength area of the multilayered film i1h mirror
  • the SiO 2 film and the TiO 2 film were set to a thickness of 97 nm and 60 nm respectively.
  • the multilayered film mirror obtained as described above had a reflectivity of about 90%.
  • the ITO electrode was formed to a thickness of ⁇ /2 (film thickness 150 nm) as an anode electrode on the multilayered film mirror.
  • Triphenylamine tetramer (TPTE) was then formed to a thickness of 60 nm as the electron hole transportation layer by a vacuum evaporation method with a degree of vacuum of 10 ⁇ 7 torr.
  • the codeposition layer of alumiquinolinol complex (Alq) and quinacridone (Qd) were formed to a thickness of 20 nm, and the Alq layer of Alq only was formed to a thickness of 35 nm as the electron transportation layer, thereby forming the luminescent layer.
  • quinacridone methylated quinacridone having high reliability was used (see the chemical formula(1)).
  • the MgAg mirror electrode was formed to a thickness of 150 nm on the luminescent layer.
  • the organic material for the luminescent layer in the above-mentioned embodiment and the example is not limited to the low-molecular material, and a macro-molecular material such as poly-para-phenylenevinylene can-also be used.
  • the present invention can further enhance the reliability of the organic EL element by covering the organic EL element of the above-mentioned embodiment with a protection film made of an organic material or an inorganic material compound, and by sealing the element by an inert gas. Sealing of the element is not limited to the use of an inert gas, and a silicon-based or fluorine-based liquid can be used for sealing.

Abstract

An optical resonator type organic electroluminescent element has a multilayered film mirror 30, a transparent electrode 12, an electron hole transportation layer 14 and a luminescent layer 16 configuring an organic layer, and a metallic electrode mirror 20, formed on a glass substrate 10. The optical resonator type organic electroluminescent element amplifies a specific wavelength (especially, in a range of about 30 nm toward a shorter wavelength side from a luminescence peak wavelength of the organic layer) in luminescence light by a minute optical resonator, which comprises the multilayered film mirror 30 and the metallic electrode mirror 20. It is determined that the minute optical resonator has an optical length L which is twice as long as a resonance wavelength, the organic layer has a thickness of 100 nm or more, and the transparent electrode has a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 Ω/□ or less. Thus, the transparent electrode can be prevented from generating heat even when a large current is caused to flow into it, and the element characteristics can be reliably prevented from being deteriorated. Moreover, the reliability of this element can be improved because the organic layer containing the luminescent layer has a sufficient thickness.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an optical resonator type organic electroluminescent element (hereafter referred to as the organic EL element), which is provided with a luminescent layer having an organic material held between a pair of electrodes, makes the luminescent layer emit light by injecting a carrier from both electrodes into the luminescent layer, and releases electromagnetic radiation in the form of light by resonating a specific wavelength in the emitted light.
2. Description of the Related Art
Research is being carried out into a flat-panel display in which the organic EL element and a plane source of light are used, as the next generation display materials, and they have attracted considerable attention. A simple dot matrix display is now being developed so as to be put to practical use. The organic EL element has a luminescent layer of an organic material formed between an anode electrode and a cathode electrode, and electrons and electron holes, which are injected from the two electrodes into the luminescent layer, are recombined therein to generate light of a fluorescence spectrum corresponding to the organic material. This light is externally emitted as a natural emitted light without directivity from the organic EL element through a glass substrate.
In order to provide such an organic EL element which can emit light with directivity, there is proposed an organic EL element having a minute optical resonator structure as shown in FIG. 1. The organic EL element having this resonator structure has an electron hole transportation layer 14 and a luminescent layer 16 of the organic material between an anode transparent electrode 12 and a cathode metallic electrode 50, and it also has a multilayered film mirror 40 between a glass substrate 10 and the anode electrode 12. The minute optical resonance structure comprises the multilayered film mirror 40 and the metallic electrode 50, and the light of a specific resonance wavelength, which is defined by a space between the multilayered film mirror 40 and the metallic electrode 50, is amplified. When a luminescent material having a broad emission spectrum is used as the organic luminescent layer 16, however, it is difficult to actually impart directivity to the luminescence light.
It is reported that the directivity of light toward the front of the element can be improved by accurately controlling the space between the multilayered film mirror 40 and the metallic electrode 50, as well as the position of a resonance wavelength, and also determining the optical length to a length of 1.5 times as long as a target wavelength λ (JPA (Hei) 9-180883).
However, the above-mentioned organic EL element having an optical length of 1.5λ had an anode transparent electrode having a thickness of about 30 nm.
Even if the transparent electrode is ITO (indium tin oxide) having a high electric conductivity, its sheet resistance is as high as 30 Ω/□, and it is impossible to prevent the generation of Joule heat. For example, when this organic EL element is used as an extremely bright backlight of a liquid crystal display device, even the most highly effective EL element requires a large inflowing current of about 100 mA/cm2 or more. The above-described element is normally driven at a current of 10 mA/cm2 or less as a display or the like. If a much larger current than that is caused to flow, heat generation in the ITO electrode cannot be avoided, and the organic EL element is heavily deteriorated as the temperature becomes higher because its deterioration is directly related to temperature. Experience shows that the lifetime of the element is decreased to {fraction (1/10)} as the driving current is increased by ten times.
For example, it is reported in Applied Physics Letter 65(15) “Sharply directed emission in organic electroluminescent diodes with an optical-microcavity structure”, Oct. 10, 1994 that use of a special luminescent material (metal complex containing a rare earth element) realizes a high directivity of light toward the front of the element by the ITO anode electrode with a thickness of 158 nm and substantially the same configuration as the conventional one.
However, the special luminescent material described in the above-mentioned document has a low luminous efficiency and unstable chemical performance. Therefore, it does not provide a highly effective element with high brightness. In addition, the organic layer has a total film thickness of 100 nm or less, and the reliability of the element is low in view of a withstand voltage or the like due to a defect or the like, and the organic layer has high probability of a local short-circuit breakdown. Thus, the above-described element is not realistic for practical use.
As described above, an optimum optical resonant organic EL element has not been provided yet, and there is not provided a resonant organic EL element which uses a luminescent material having high luminous efficiency and has high reliability at a large current. Besides, the satisfactory directivity of light toward the front of the element has not been achieved.
SUMMARY OF THE INVENTION
The present invention was achieved to solve the above-mentioned problems, and it is an object of the invention to improve the luminous efficiency and reliability of an organic EL element.
To achieve the above-mentioned object, an organic electroluminescent element having a minute optical resonator for amplifying a specific wavelength in a luminescence light comprising a substrate; a multilayered film mirror formed of laminated layers on the substrate, each of the layers having a different refractive index; a transparent electrode as an anode on the multilayered film mirror; an organic layer on the transparent electrode; and a metallic electrode mirror as a cathode on the organic layer, said organic layer comprising a luminescent layer for emitting a light by injecting electron holes and electrons through the transparent electrode and the metallic electrode mirror, said multilayered film mirror and said metallic electrode mirror constituting a minute optical resonator for amplifying a specific wavelength in the light, wherein the minute optical resonator has an optical length twice as long as a target amplified wavelength, the organic layer is not less than 100 nm thick, and the transparent electrode is not less than 50 nm thick, or is of not more than 30 Ω in sheet resistance.
The “optical length” of the minute optical resonator is determined by a soaked quantity of light into the multilayered film mirror and an optical thickness of the organic layer (Document: J. Appl. Phys., 80 (1996) 6954). The optical length is determined to be twice-as long as a target amplified wavelength λ so to make it possible for the anode transparent electrode and the organic layer to have an appropriate thickness in view of the characteristics of the element.
Specifically, it is characterized by determining the organic layer to have a thickness of 100 nm or more, and the transparent electrode to have a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 Ω/□ or less. The reliability of the organic layer is improved by determining its thickness to 100 nm or more. Heat generation due to a large current flowing through the element can be suppressed by setting the transparent electrode to have a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 Ω/□ or less. Thus, the characteristics of the element can be prevented from being deteriorated due to heat generation, and the element can be driven at a large current and readily employed as a lighting device with high brightness.
Moreover, it is suitable in this invention to adjust the above-mentioned target amplified wavelength in a range of about 30 nm toward the side of a shorter wavelength from the luminescence peak wavelength of the luminescent layer.
Because a satisfactory emission intensity or high directivity cannot be obtained if the target amplified wavelength is more than 30 nm away from the luminescence peak wavelength of the luminescent layer, the conditions described above are preferably determined so that a satisfactory emission intensity can be obtained, and light having high directivity can be emitted from the element.
It is more suitable to set the transparent electrode to have an optical thickness of λ/2 for example. Here, an optical thickness L of the film is expressed in L=D×n (n: a refractive index) with respect to an actual thickness D of the film. By setting it as described above, the transparent electrode has an actual thickness of about 129 nm (actual thickness is a value resulting from dividing the optical thickness by its refractive index (=1.93)) when the target amplified wavelength λ is for example 500 nm, and a sheet resistance of about 15 Ω/□ can be achieved.
Moreover, it is desirable to use the luminescent material with a narrow emission spectrum to configure the organic layer in order to additionally enhance the luminescence color purity of the organic EL element. For example, it is desirable to use a luminescent material such as quinacridone having a half-width of about 80 nm or less.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the configuration of a general minute optical resonator type organic EL element;
FIG. 2 is a diagram showing the configuration of the minute optical resonator type organic EL element according to Embodiment 1 of the present invention;
FIG. 3 is a diagram showing brightness and current characteristics of the organic EL element of the invention compared with that of a conventional organic EL element for brightness and current characteristics;
FIGS. 4A and 4B are conceptual diagrams for illustrating differences of characteristics between the organic EL element of the invention and the conventional organic EL element due to the structural differences;
FIG. 5 is a diagram showing a positional relationship between the emission spectrum and the resonance wavelength of the luminescent layer of the minute optical resonator type organic EL element according to the embodiment of the invention;
FIG. 6 is a diagram showing the emission spectrum of the minute optical resonator type organic EL element when quinacridone is used as the luminescent layer;
FIG. 7 is a diagram showing the emission spectrum of the minute optical resonator type organic. EL element when alumiquinolinol complex is used as the luminescent layer;
FIG. 8 is a diagram showing an emission spectrum of the luminescent layer and its angle dependency;
FIG. 9A is a diagram showing a position of the target amplified wavelength determined with respect to the peak wavelength of the emission spectrum of the luminescent layer;
FIG. 9B and FIG. 9C are diagrams illustrating characteristics of the emitted light obtained when the target amplified wavelength is determined as shown in FIG. 9A;
FIG. 10A and FIG. 10B are diagrams illustrating an emission intensity and directivity of the emitted light obtained when the target amplified wavelength is determined to be on the side of a longer wavelength of the peak wavelength of the emission spectrum of the luminescent layer; and
FIG. 11 is a diagram showing the configuration of the minute optical resonator type organic EL element according to an example of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will be described with reference to the accompanying drawings.
FIG. 2 is a diagram showing the configuration of the minute optical resonator type organic EL element according to this embodiment-. The organic EL element of this embodiment has a multilayered film mirror (dielectric mirror) 30, which is formed by laminating two kinds of layers having a different refractive index into a plurality of layers, formed on a glass substrate 10. A transparent electrode 12 using ITO (indium tin oxide), SnO2, ln2O3 or the like is formed as an anode on the multilayered film mirror 30. Moreover., an organic layer, which contains a luminescent layer 16 and an electron. hole transportation layer 14, is formed on the transparent electrode 12, and a metallic electrode mirror 20 is formed of Ag, MgAg, AlLi or Al with LiF as a cathode electrode on the organic layer.
A minute optical resonator comprises the multilayered film mirror 30 and the metallic electrode mirror 20, and its optical length is a sum of a quantity of light soaked into the multilayered film mirror 30 and an optical thickness of the transparent electrode 12 and the organic layer. In this embodiment, the optical length is set to twice as long as a target amplified wavelength (resonance wavelength) λ, and the transparent electrode 12 is determined to have a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 Ω/□ or less. In addition, the organic layer is determined to have a total thickness (the total thickness of the luminescent layer 16 and the electron hole transportation layer 14) 100 nm or more.
The sheet resistance becomes 30 Ω/□ or more even if ITO is used as the transparent electrode when the optical length is 1.5λ and the transparent electrode has a thickness of about 30 nm as in the conventional art. Meanwhile, it is determined in this embodiment that the optical length is two times longer than the target amplified wavelength λ, and the transparent electrode 12 has a thickness of 50 nm or more or a thickness so to have a sheet resistance of 30 Ω/□ or less.
Especially, it is desirable to determine the transparent electrode 12 to have a thickness of λ/2. When the transparent electrode 12 has a thickness of λ/2 as above, its resistance can be decreased to half, and the Joule heat generated in the transparent electrode 12 using ITO can be decreased to ¼ even by a simple calculation. FIG. 3 shows the brightness and current characteristics of the element when the ITO transparent electrode as a thickness of λ/4 or less as. in the conventional art and those of the element when ITO is used as the transparent electrode 12 and its thickness is λ/2 as in the present embodiment. When a large current is caused to flow through the conventional element, it is deteriorated by the Joule heat to lower its brightness. However, the element of this embodiment is hardly deteriorated by having a large current flow, and higher luminescence brightness is obtained with the increase of the amount of the current. Thus, the element can be reliably prevented from having an increased temperature by increasing the thickness of the transparent electrode 12 so to have a very low sheet resistance, and stable light emission with high brightness can be carried out for a long time.
Moreover, the entire organic layer is determined so as to have a thickness of 100 nm or more so that a local short-circuit breakdown in the organic EL element can be prevented, and the reliability of the element is secured.
FIG. 4A and FIG. 4B conceptually show differences of actions between the resonator type organic EL element having an optical length of 1.5λ and the resonator type organic EL element having an optical length of 2λ as in this embodiment. As shown in FIG. 4A, the element having the optical length of 1.5λ may have a high resistance because the transparent electrode 12 is thin, and since the organic layer is thin in addition, the transparent electrode 12 and the metallic electrode 50 might be partially short-circuited due to projections of the electrode layer or adhesion of dust or the like. One of the reasons that the conventional element has a short lifetime is that such a short-circuit is caused with a lapse of driving time. On the other hand, as shown in FIG. 4B, the element of this embodiment has an optical length of 2λ, and the transparent electrode 12 and the organic layer also have a sufficient thickness as described above. Therefore, it is unlikely that the electrodes are short-circuited due to the presence of dust or the projections of the electrode layer. In view of the reasons described above, the element of this embodiment can have a long service lifetime as described above.
When the optical length is 2λ as described above, a resonance mode m to be used becomes 4, namely a fourth mode in view of the optical length L=m·λ/2 In this case, a low luminescence peak (low-level mode), for example, the resonance mode of m=3, 5, is generated near the use mode as shown in FIG. 5. Also, when it is set to overlap with a steep area on the shorter wavelength side of the emission 1 spectrum of the luminescent material which uses the fourth target amplified wavelength, the resonance wavelength of the third mode appears on the long wavelength side of the fourth mode. Then, it is desirable to use the former luminescent material having a narrow spectrum for the luminescent layer 16 so that no other low-level mode should enter the emission spectrum. In other words, the luminescent material has a small half-width of the emission spectrum (a width with which the maximum peak value becomes half).
For example, the luminescent material to be used preferably has an emission spectrum not overlapping with 650 nm and a half-width of 80 nm or less. The luminescent material satisfying the requirements described above contains quinacridone (half-width of 80 nm) expressed by the following chemical formula (1) for example.
Figure US06406801-20020618-C00001
FIG. 6 shows a relationship between a wavelength and an emission intensity (left vertical axis) under conditions that a target amplified wavelength is determined to 535 nm, the luminescent material containing the above-mentioned quinacridone is used as the luminescent layer, the organic layer has a thickness of 140 nm and the ITO electrode has a thickness of 150 nm. FIG. 7 shows a relationship between a wavelength and an emission intensity (left vertical axis) under conditions that the target amplified wavelength is 500 nm, the luminescent layer is Alq, the organic layer has a thickness of 115 nm, the ITO electrode has a thickness of 150 nm, and an SiO2film and a Tio2 film are each formed in four layers to configure the multilayered film mirror. Right vertical axes in FIG. 6 and FIG. 7 show resonance strengths (arbitrary unit a.u.) with m=5, 4 and 3.
As indicated by the dotted line in FIG. 6, quinacridone has an emission spectrum of 650 nm or less and a half-width of 80 nm or less, and its spectrum does not overlap with the third peak generated in the neighborhood of 720 nm. Therefore, the emission spectrum of the resonant organic EL element finally obtained has its set wavelength in the neighborhood of 535 nm selectively amplified as indicated by broken chain line in FIG. 6. When alumiquinolinol complex (Alq) indicated by the chemical formula (2) below is used, its emission spectrum has a large half-width and the spectrum also exists in the vicinity of 650 nm as indicated by a dotted line in FIG. 7. Also, the resonance wavelength of the third mode has been m0 contained in this emission spectrum. Therefore, the optical resonant organic EL element using Alq as the luminescent layer also emits at the resonance wavelength of the third mode as indicated by broken chain line in FIG. 7. Therefore, color purity is lowered, and the directivity toward the front of the element can not be obtained.
Figure US06406801-20020618-C00002
Because a red luminescent element in a low-level mode emits in an infrared region (700 nm or more), a luminescent material with a large half-width can be used without involving any problem in a visual (for non-visual light for person).
As a material for the luminescent layer 16, for example, perylene expressed by the chemical formula (3), an oxadiazol-based material expressed by the chemical formula (4), or distilarylene)-based material expressed by the chemical formula (5) can be used to emit blue light. Phthalocyanine expressed by the chemical formula (6) or DCM2(5) expressed by the chemical formula (7) can be used to emit red light.
Figure US06406801-20020618-C00003
Moreover, the electron hole transportation layer 14, which constitutes the organic layer with the luminescent layer 16, is mainly composed of an aromatic amine-based material, such as TPTE (triphenylamine tetramer) expressed by the chemical formula (8) or α-NPB(Bis[N-(1-naphthyl)-N-phenyl] benzidine).
Figure US06406801-20020618-C00004
Moreover, the organic layer comprises the luminescent layer and the electron hole transportation layer. In order to further facilitate the injection of the electrons into the luminescent layer, it is preferable that an electron transportation layer using an organic material is formed between the luminescent layer and the metallic electrode mirror or an electron injection layer which consists of the oxide or fluoride of alkaline metal or alkaline-earth metal is formed therebetween.
In this embodiment, the target amplified wavelength is determined to be about 30 nm toward the short wavelength side of the emitted peak wavelength of the luminescent layer as described above, and the reasons for doing so are given below.
The target amplified wavelength is a wavelength (resonance wavelength) resonant with the resonator (organic EL element) and variable depending on an angle that it is observed. For example, as shown in FIG. 8, when the observing direction is changed from the front (θ=0°) of the resonator to its diagonal direction (e.g., θ=30°, 60°), the target amplified wavelength shifts toward the shorter wavelength side. Accordingly, when the target amplified wavelength is determined to be positioned far away from the luminescence peak of the luminescent layer, the emission intensity (amplified light intensity) lowers, and the directivity is lost as the whole. For example, when the emission spectrum of the luminescent layer has the characteristics as indicated by the solid line in FIG. 9A and the target amplified wavelength is determined to be at position (α) longer than 30 nm toward the shorter wavelength side from the luminescence peak, the directivity of the emitted light from the resonant organic EL element is very small as shown in FIG. 9B. Meanwhile, when the target amplified wavelength is determined on the longer wavelength side from the luminescence peak, such as position (β), as shown in FIG. 9A, the directivity is lost as shown in FIG. 9C. Besides, when the target amplified wavelength is largely separated toward the long wavelength side from the luminescence peak, the emission spectrum itself of the luminescent layer in that region is small, so that the emitted light intensity itself at the front of the element also becomes small.
The directivity of the emitted light obtained by resonating becomes higher as the material for the luminescent layer has a steeper property on the short wavelength side of the luminescence peak. As described above, this embodiment uses a luminescent material which has as steep a luminescence property as possible for the luminescent layer. Accordingly, the intensity of the emission spectrum of the luminescent layer itself is extremely small at a position more than 30 nm away toward the short wavelength side from the luminescence peak, and a satisfactory emission intensity cannot be obtained even if such a wavelength is determined as the target amplified wavelength. For example, in FIG. 6, quinacridone Qd has a luminescence peak wavelength of 540 nm, the short wavelength side 30 nm away from there is 510 nm, where the emission intensity of the original emission spectrum is only {fraction (1/30)} of the peak strength. Therefore, the target amplified wavelength is preferably determined to fall in a range of within 30 nm toward the short wavelength side from the luminescence peak wavelength.
By determining the target amplified wavelength to be within about 30 nm toward the long wavelength side from the luminescence peak wavelength, emission of light itself can be obtained, but the directivity is not obtained as shown in FIG. 9C as described above. FIGS. 10A and 10B specifically show the state described above. As shown in FIG. 10A, when the target amplified wavelength is determined on the long wavelength side of the luminescent layer and the observing direction is changed to shift the wavelength of the emitted light with the target amplified wavelength to the short wavelength side as described above, a region having a high emission intensity containing the luminescence peak of the original emission spectrum of the luminescent layer is on the short wavelength side of the shifted target amplified wavelength. Accordingly, as shown in FIGS. 10A and 10B, the emission intensity at oblique angles (e.g.,θ=30°, 45°, 60°) also becomes high with respect to the emission intensity observed at the front (θ=0°) of the resonant organic EL element. In other words, when observed obliquely, light with the corresponding wavelength having a high emission intensity is observed, and sufficient directivity toward the front of the element cannot be obtained. Thus, it becomes necessary to separately split the light being emitted from the element.
As described above, the satisfactory emission intensity and directivity can be obtained by determining the target amplified wavelength to be within 30 nm on the short wavelength side of the luminescence peak of the luminescent layer.
EXAMPLE
FIG. 11 shows an example of the organic EL element of the present invention. In the organic EL element shown in FIG. 11, the multilayered film mirror was first formed on a cleaned glass substrate by alternately forming the SiO2 film and the TiO2 film each having a different refractive index (alternately four layers each to form eight layers in total) by a magnetron sputtering method. Here, a stop band (optical reflected wavelength area of the multilayered film i1h mirror) was set to a center wavelength of 570 nm, and the SiO2 film and the TiO2 film were set to a thickness of 97 nm and 60 nm respectively. The multilayered film mirror obtained as described above had a reflectivity of about 90%.
Next, the ITO electrode was formed to a thickness of λ/2 (film thickness 150 nm) as an anode electrode on the multilayered film mirror. Triphenylamine tetramer (TPTE) was then formed to a thickness of 60 nm as the electron hole transportation layer by a vacuum evaporation method with a degree of vacuum of 10−7 torr. In addition, the codeposition layer of alumiquinolinol complex (Alq) and quinacridone (Qd) were formed to a thickness of 20 nm, and the Alq layer of Alq only was formed to a thickness of 35 nm as the electron transportation layer, thereby forming the luminescent layer. As for quinacridone, methylated quinacridone having high reliability was used (see the chemical formula(1)). Finally, the MgAg mirror electrode was formed to a thickness of 150 nm on the luminescent layer.
By applying a voltage of 5V DC to between the ITO electrode and the MgAg mirror electrode of the organic EL element obtained as described above, a green luminescence having directivity toward the front of the element (lower side of FIG. 11) was obtained. The brightness of 30000 cd/m2 was obtained when the drive voltage was raised to have the injection current of 500 mA/cm2 (15V) into the luminescent layer, while the directivity toward the front of the element was maintained. Moreover, the lifetime of the element until the brightness was reduced to half could be improved to ten hours.
The organic material for the luminescent layer in the above-mentioned embodiment and the example is not limited to the low-molecular material, and a macro-molecular material such as poly-para-phenylenevinylene can-also be used.
In addition, the present invention can further enhance the reliability of the organic EL element by covering the organic EL element of the above-mentioned embodiment with a protection film made of an organic material or an inorganic material compound, and by sealing the element by an inert gas. Sealing of the element is not limited to the use of an inert gas, and a silicon-based or fluorine-based liquid can be used for sealing.
While there have been described what are at present considered to be preferred embodiments of the invention, it is to be understood that various modifications may be made thereto, and it is intended that the appended claims cover all such modifications as fall within the true spirit and scope of the invention.

Claims (8)

What is claimed is:
1. An organic electroluminescent element having a minute optical resonator for amplifying a specific wavelength in a luminescence light comprising:
a substrate;
a multilayered film mirror formed between the substrate and said transparent electrode, each film having a different refractive index;
a transparent electrode as an anode on the multilayered film mirror;
an organic layer on the transparent electrode; and
a metallic electrode mirror as a cathode on the organic layer,
said organic layer comprising a luminescent layer for emitting a light by injecting holes and electrons through the transparent electrode and the metallic electrode mirror,
said multilayered film mirror and said metallic electrode mirror constituting a minute optical resonator for amplifying a specific wavelength in the light, wherein
the minute optical resonator has an optical length twice as long as a target amplified wavelength, the organic layer is not less than 100 nm thick, and the transparent electrode is not less than 50 nm thick, or is of not more than 30 Ω in sheet resistance;
the luminescent material of said luminescent layer has an emission spectrum with no luminescence component in a wavelength region of low order luminescence peak other than said target amplified wavelength; and
the target amplified wavelength is in a range of about 30 nm toward a shorter wavelength side from a luminescence peak wavelength of the luminescent layer to a luminescence peak wavelength of the luminescent layer.
2. The organic electroluminescent element according to claim 1, wherein the transparent electrode has an optical thickness L of λ/2 with respect to the target amplified wavelength λ provided that L is expressed as L=D×n wherein D is an actual film thickness D of the transparent electrode, and n is a refractive index of the transparent electrode.
3. The organic electroluminescent element according to claim 1, wherein the luminescent spectrum width is about 80 nm or less in half-width.
4. The organic electroluminescent element according to claim 1, wherein the luminescent layer comprises quinacridone.
5. The organic electroluminescent element according to claim 1, wherein the organic layer is not less than 115 nmn thick.
6. The organic electroluminescent element according to claim 1, wherein the thickness of the transparent electrode is greater than λ/4 and said optical thickness L satisfies the relationship L=D×n where D is the actual film thickness D.
7. An organic electroluminescent element having a minute optical resonator for amplifying a specific wavelength in a luminescence light comprising:
a substrate;
a multilayered film mirror formed on the substrate;
a transparent electrode as an anode on the multilayered film mirror;
an organic layer on the transparent electrode; and
a metallic electrode mirror as a cathode on the organic layer,
said organic layer comprising a luminescent layer for emitting a light by injecting holes and electrons through the transparent electrode and the metallic electrode mirror,
said multilayered film mirror and said metallic electrode mirror constituting a minute optical resonator for amplifying a specific wavelength in the light, wherein
the minute optical resonator has an optical length twice as long as a target amplified wavelength;
the organic layer is not less than 100 nm thick;
the transparent electrode is not less than 50 nm thick, or is of not more than 30 Ω in sheet resistance; and
said target amplified wavelength is set so that the wavelength region of low order luminescence peak other than said target amplified wavelength is located outside the visual light region.
8. An organic electroluminescent element having a minute optical resonator for amplifying a specific wavelength in a luminescence light comprising:
a substrate;
a multilayered film mirror formed of laminated layers on the substrate, each of the layers having a different refractive index;
a transparent electrode as an anode on the multilayered film mirror;
an organic layer on the transparent electrode; and
a metallic electrode mirror as a cathode on the organic layer,
said organic layer comprising a luminescent layer for emitting a light by injecting holes and electrons through the transparent electrode and the metallic electrode mirror,
said multilayered film mirror and said metallic electrode mirror constituting a minute optical resonator for amplifying a specific wavelength in the light, wherein
the minute optical resonator has an optical length twice as long as a target amplified wavelength, the organic layer is not less than 100 nm thick, and the transparent electrode is not less than 50 nm thick, or is of not more than 30 Ω in sheet resistance; and
the transparent electrode has an optical thickness L of λ/2 with respect to the target amplified wavelength λ provided that L is expressed as L=D×n, wherein D is an actual film thickness D of the transparent electrode, and n is a refractive index of the transparent electrode.
US09/243,479 1998-02-04 1999-02-03 Optical resonator type organic electroluminescent element Expired - Fee Related US6406801B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP10-023692 1998-02-04
JP2369298 1998-02-04
JP11017978A JPH11288786A (en) 1998-02-04 1999-01-27 Optical resonance type organic electroluminescence element
JP11-017978 1999-01-27

Publications (1)

Publication Number Publication Date
US6406801B1 true US6406801B1 (en) 2002-06-18

Family

ID=26354584

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/243,479 Expired - Fee Related US6406801B1 (en) 1998-02-04 1999-02-03 Optical resonator type organic electroluminescent element

Country Status (2)

Country Link
US (1) US6406801B1 (en)
JP (1) JPH11288786A (en)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040051447A1 (en) * 2002-09-12 2004-03-18 Canon Kabushiki Kaisha Organic electroluminescent display and apparatus including organic electroluminescent display
US20040140757A1 (en) * 2003-01-17 2004-07-22 Eastman Kodak Company Microcavity OLED devices
US20040149984A1 (en) * 2003-01-31 2004-08-05 Eastman Kodak Company Color OLED display with improved emission
US20040155576A1 (en) * 2003-01-17 2004-08-12 Eastman Kodak Company Microcavity OLED device
US20040160172A1 (en) * 2003-02-18 2004-08-19 Eastman Kodak Company Tuned microcavity color OLED display
US20040161004A1 (en) * 2003-02-18 2004-08-19 Eastman Kodak Company Organic laser having improved linearity
US20050040756A1 (en) * 2003-08-19 2005-02-24 Eastman Kodak Company OLED device having microcavity gamut subpixels and a within gamut subpixel
US20050095459A1 (en) * 2002-06-28 2005-05-05 Chin Byung D. Organic electroluminescent device using a mixture of high and low molecular light-emitting substances as a light-emitting substance
US6917159B2 (en) 2003-08-14 2005-07-12 Eastman Kodak Company Microcavity OLED device
US20050212414A1 (en) * 2004-03-25 2005-09-29 Noriyuki Matsusue Light emitting display apparatus with slight color shifting
US20050225233A1 (en) * 2004-04-08 2005-10-13 Eastman Kodak Company OLED with color change media
US20050249972A1 (en) * 2004-05-04 2005-11-10 Eastman Kodak Company Tuned microcavity color OLED display
US20060066228A1 (en) * 2004-09-28 2006-03-30 Homer Antoniadis Reducing or eliminating color change for microcavity OLED devices
US20060070014A1 (en) * 2004-09-27 2006-03-30 Taiwan Semiconductor Manufacturing Company, Ltd. Real time monitoring system of semiconductor manufacturing information
US7023013B2 (en) 2004-06-16 2006-04-04 Eastman Kodak Company Array of light-emitting OLED microcavity pixels
US20060097630A1 (en) * 2004-11-10 2006-05-11 Pentax Corporation Organic electroluminescent device and process for producing this same
US20060103321A1 (en) * 2002-06-28 2006-05-18 Helmut Bechtel Electroluminescent device with a transparent cathode
US20060115678A1 (en) * 2004-11-26 2006-06-01 Canon Kabushiki Kaisha Aminoanthryl derivative-substituted pyrene compound and organic light-emitting device
US20060206224A1 (en) * 2005-03-10 2006-09-14 Eastman Kodak Company Selecting OLED devices using figure of merit
US20070046183A1 (en) * 2005-08-29 2007-03-01 Kwok Hoi S Metallic anode treated by carbon tetrafluoride plasma for organic light emitting device
US20070063641A1 (en) * 2005-09-22 2007-03-22 Eastman Kodak Company OLED device having improved light output
US20070096641A1 (en) * 2002-04-09 2007-05-03 Canon Kabushiki Kaisha Organic luminescence device with anti-reflection layer and organic luminescence device package
US7245065B2 (en) 2005-03-31 2007-07-17 Eastman Kodak Company Reducing angular dependency in microcavity color OLEDs
US20080129191A1 (en) * 2006-12-04 2008-06-05 Sung-Hun Lee High efficiency organic light emitting device
US20080238308A1 (en) * 2005-10-14 2008-10-02 Franky So Method and Apparatus for Light Emission Utilizing an OLED with a Microcavity
US20080284320A1 (en) * 2005-06-15 2008-11-20 Braggone Oy Optical Device Structure
US20090026921A1 (en) * 2005-03-11 2009-01-29 Idemitsu Kosan Co., Ltd. Organic electroluminescent color light-emitting device
US20090179563A1 (en) * 2008-01-11 2009-07-16 Seiko Epson Corporation Light-emitting apparatus and electronic apparatus
US20100059780A1 (en) * 2008-09-10 2010-03-11 Tpo Displays Corp. System for displaying images
US20100219427A1 (en) * 2007-11-14 2010-09-02 Canon Kabushiki Kaisha Light-emitting apparatus
US20110079772A1 (en) * 2008-01-18 2011-04-07 Astron Fiamm Safety Organic light-emitting diode with microcavity including doped organic layers and fabrication process thereof
CN102201543A (en) * 2010-03-26 2011-09-28 富士胶片株式会社 Organic electric field luminous element and organic electric field luminescent display using the same
CN102217421A (en) * 2008-12-26 2011-10-12 松下电器产业株式会社 Organic el element, organic el display device, and method for manufacturing organic el element
US8339033B2 (en) 2009-06-11 2012-12-25 Pioneer Corporation Light emitting element and display device
WO2014083693A1 (en) * 2012-11-30 2014-06-05 パイオニア株式会社 Light emitting device
US8912532B2 (en) 2009-04-07 2014-12-16 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Patterning the emission colour in top-emissive OLEDs
US9185772B2 (en) 2009-07-28 2015-11-10 Pioneer Corporation Light-emitting element and display device
CN112242493A (en) * 2019-07-17 2021-01-19 密西根大学董事会 Organic light emitting device
US11557747B2 (en) 2018-11-12 2023-01-17 Wuhan Tianma Micro-Electronics Co., Ltd. Display device

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000323279A (en) * 1999-03-10 2000-11-24 Fuji Photo Film Co Ltd Organic luminescent element for exposure light source
EP1154676A4 (en) * 1999-11-22 2008-08-20 Sony Corp Display device
JP2001223086A (en) * 2000-02-10 2001-08-17 Fuji Photo Film Co Ltd Organic light emitting element and image formation method using it
JP2001267074A (en) * 2000-03-22 2001-09-28 Fuji Photo Film Co Ltd Organic light emission element
JP3508741B2 (en) * 2001-06-05 2004-03-22 ソニー株式会社 Display element
JP3650073B2 (en) 2002-03-05 2005-05-18 三洋電機株式会社 Organic electroluminescence device and method for manufacturing the same
JP4378366B2 (en) * 2005-08-04 2009-12-02 キヤノン株式会社 Light emitting element array
WO2009064019A1 (en) * 2007-11-14 2009-05-22 Canon Kabushiki Kaisha Light-emitting apparatus
JP5309388B2 (en) * 2008-02-27 2013-10-09 株式会社日立製作所 Self-luminous element and display device
JP5210267B2 (en) * 2009-09-04 2013-06-12 ユー・ディー・シー アイルランド リミテッド Organic electroluminescent device and manufacturing method thereof
FR2957718B1 (en) * 2010-03-16 2012-04-20 Commissariat Energie Atomique HYBRID HIGH PERFORMANCE ELECTROLUMINESCENT DIODE
JP6111478B2 (en) * 2012-07-04 2017-04-12 株式会社Joled Light emitting element and display device
KR102156345B1 (en) * 2014-05-14 2020-09-15 엘지디스플레이 주식회사 Organic Light Emitting Diode and Display device including the same
JP2016213052A (en) 2015-05-08 2016-12-15 株式会社Joled Blue organic el element, organic el display panel, and method for manufacturing blue organic el element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007344A1 (en) 1992-09-22 1994-03-31 Hitachi, Ltd. Organic luminescent element and its substrate
JPH06275381A (en) 1993-03-18 1994-09-30 Hitachi Ltd Multicolor luminous element and substrate thereof
JPH06283270A (en) 1993-03-26 1994-10-07 Hitachi Ltd Organic light resonator element made in high vacuum
JPH09180883A (en) 1995-10-27 1997-07-11 Toyota Central Res & Dev Lab Inc Micro-light resonating organic electroluminescent element
US5780174A (en) 1995-10-27 1998-07-14 Kabushiki Kaisha Toyota Chuo Kenkyusho Micro-optical resonator type organic electroluminescent device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3586906B2 (en) * 1994-12-14 2004-11-10 凸版印刷株式会社 Method for manufacturing transparent conductive film
JP2838063B2 (en) * 1995-09-20 1998-12-16 出光興産株式会社 Organic electroluminescence device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994007344A1 (en) 1992-09-22 1994-03-31 Hitachi, Ltd. Organic luminescent element and its substrate
JPH06275381A (en) 1993-03-18 1994-09-30 Hitachi Ltd Multicolor luminous element and substrate thereof
JPH06283270A (en) 1993-03-26 1994-10-07 Hitachi Ltd Organic light resonator element made in high vacuum
JPH09180883A (en) 1995-10-27 1997-07-11 Toyota Central Res & Dev Lab Inc Micro-light resonating organic electroluminescent element
US5780174A (en) 1995-10-27 1998-07-14 Kabushiki Kaisha Toyota Chuo Kenkyusho Micro-optical resonator type organic electroluminescent device

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
A. Dodabalapur, et al., "Electroluminescence From Organic Semiconductors in Patterned Microcavities", Electronics Letters, vol. 30 No. 12, Jun. 9, 1994, pp. 1000-1002.
A. Dodabalapur, et al., "Physics and Applications of Organic Microcavity Light Emitting Diodes", J. Appl. Phys. 80 (12), Dec. 15, 1996, pp. 6954-6964.
Noriyuki Takada, et al., "Control of Emission Characteristics in Organic Thin-Film Electroluminescent Diodes Using and Optical-Microcavity Structure", Appl. Phys. Lett. 63 (15), Oct. 11, 1993, pp. 2032-2034.
S. Tokito, et al., "High Performance Organic Electroluminescent Diodes with Microcavities", Electronics Letters, vol. 32 No. 7, Mar. 28, 1996, pp. 691-692.
Takahiro Nakayama, et al., "Organic Photo- and electroluminescent Devices With Double Mirrors", Appl. Phys. Lett. 63 (5), Aug. 2, 1993, pp. 594-595.
Tetsuo Tsutsui, et al., "Sharply Directed Emission in Organic Electroluminescent Diodes with an Optical-Microcavity Structure", Appl. Phys. Lett., 65 (15), Oct. 10, 1994, pp. 19-21.

Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070096641A1 (en) * 2002-04-09 2007-05-03 Canon Kabushiki Kaisha Organic luminescence device with anti-reflection layer and organic luminescence device package
US20060103321A1 (en) * 2002-06-28 2006-05-18 Helmut Bechtel Electroluminescent device with a transparent cathode
US7642714B2 (en) * 2002-06-28 2010-01-05 Koninklijke Philips Electronics, N.V. Electroluminescent device with a transparent cathode
CN1666354B (en) * 2002-06-28 2010-06-16 皇家飞利浦电子股份有限公司 Electroluminescent device with a transparent cathode
US20050095459A1 (en) * 2002-06-28 2005-05-05 Chin Byung D. Organic electroluminescent device using a mixture of high and low molecular light-emitting substances as a light-emitting substance
US7875308B2 (en) 2002-06-28 2011-01-25 Samsung Mobile Display Co., Ltd. Organic electroluminescent device using a mixture of high and low molecular light-emitting substances as a light-emitting substance
US7355339B2 (en) 2002-09-12 2008-04-08 Canon Kabushiki Kaisha Organic electroluminescent display and apparatus including organic electroluminescent display
US20040051447A1 (en) * 2002-09-12 2004-03-18 Canon Kabushiki Kaisha Organic electroluminescent display and apparatus including organic electroluminescent display
US20040140757A1 (en) * 2003-01-17 2004-07-22 Eastman Kodak Company Microcavity OLED devices
US20040155576A1 (en) * 2003-01-17 2004-08-12 Eastman Kodak Company Microcavity OLED device
US20040149984A1 (en) * 2003-01-31 2004-08-05 Eastman Kodak Company Color OLED display with improved emission
US20040161004A1 (en) * 2003-02-18 2004-08-19 Eastman Kodak Company Organic laser having improved linearity
US6870868B2 (en) * 2003-02-18 2005-03-22 Eastman Kodak Company Organic laser having improved linearity
US6861800B2 (en) 2003-02-18 2005-03-01 Eastman Kodak Company Tuned microcavity color OLED display
US20040160172A1 (en) * 2003-02-18 2004-08-19 Eastman Kodak Company Tuned microcavity color OLED display
US6917159B2 (en) 2003-08-14 2005-07-12 Eastman Kodak Company Microcavity OLED device
US20050040756A1 (en) * 2003-08-19 2005-02-24 Eastman Kodak Company OLED device having microcavity gamut subpixels and a within gamut subpixel
US7030553B2 (en) 2003-08-19 2006-04-18 Eastman Kodak Company OLED device having microcavity gamut subpixels and a within gamut subpixel
US20050212414A1 (en) * 2004-03-25 2005-09-29 Noriyuki Matsusue Light emitting display apparatus with slight color shifting
US7508005B2 (en) * 2004-03-25 2009-03-24 Sanyo Electric Co., Ltd. Light emitting display apparatus with slight color shifting
US7057339B2 (en) * 2004-04-08 2006-06-06 Eastman Kodak Company OLED with color change media
US20050225233A1 (en) * 2004-04-08 2005-10-13 Eastman Kodak Company OLED with color change media
US7247394B2 (en) 2004-05-04 2007-07-24 Eastman Kodak Company Tuned microcavity color OLED display
US20050249972A1 (en) * 2004-05-04 2005-11-10 Eastman Kodak Company Tuned microcavity color OLED display
US7023013B2 (en) 2004-06-16 2006-04-04 Eastman Kodak Company Array of light-emitting OLED microcavity pixels
US20060070014A1 (en) * 2004-09-27 2006-03-30 Taiwan Semiconductor Manufacturing Company, Ltd. Real time monitoring system of semiconductor manufacturing information
US7489074B2 (en) 2004-09-28 2009-02-10 Osram Opto Semiconductors Gmbh Reducing or eliminating color change for microcavity OLED devices
US20060066228A1 (en) * 2004-09-28 2006-03-30 Homer Antoniadis Reducing or eliminating color change for microcavity OLED devices
US20060097630A1 (en) * 2004-11-10 2006-05-11 Pentax Corporation Organic electroluminescent device and process for producing this same
US20060115678A1 (en) * 2004-11-26 2006-06-01 Canon Kabushiki Kaisha Aminoanthryl derivative-substituted pyrene compound and organic light-emitting device
US7709104B2 (en) 2004-11-26 2010-05-04 Canon Kabushiki Kaisha Aminoanthryl derivative-substituted pyrene compound and organic light-emitting device
US7236845B2 (en) 2005-03-10 2007-06-26 Eastman Kodak Company Selecting OLED devices using figure of merit
US20060206224A1 (en) * 2005-03-10 2006-09-14 Eastman Kodak Company Selecting OLED devices using figure of merit
US7956529B2 (en) * 2005-03-11 2011-06-07 Idemitsu Kosan Co., Ltd. Organic electroluminescent color light-emitting apparatus with organic electroluminescent devices with adjusted optical distances between electrodes
TWI411350B (en) * 2005-03-11 2013-10-01 Idemitsu Kosan Co Organic electroluminescent light - emitting device
US20090026921A1 (en) * 2005-03-11 2009-01-29 Idemitsu Kosan Co., Ltd. Organic electroluminescent color light-emitting device
US7245065B2 (en) 2005-03-31 2007-07-17 Eastman Kodak Company Reducing angular dependency in microcavity color OLEDs
US20080284320A1 (en) * 2005-06-15 2008-11-20 Braggone Oy Optical Device Structure
US10690847B2 (en) * 2005-06-15 2020-06-23 Braggone Oy Method of making a photonic crystal device and photonic crystal device
US20070046183A1 (en) * 2005-08-29 2007-03-01 Kwok Hoi S Metallic anode treated by carbon tetrafluoride plasma for organic light emitting device
US9166197B2 (en) 2005-08-29 2015-10-20 The Hong Kong University Of Science And Technology Metallic anode treated by carbon tetrafluoride plasma for organic light emitting device
US20070063641A1 (en) * 2005-09-22 2007-03-22 Eastman Kodak Company OLED device having improved light output
US7719182B2 (en) 2005-09-22 2010-05-18 Global Oled Technology Llc OLED device having improved light output
US8987985B2 (en) * 2005-10-14 2015-03-24 University Of Florida Foundation, Inc. Method and apparatus for light emission utilizing an OLED with a microcavity
US20080238308A1 (en) * 2005-10-14 2008-10-02 Franky So Method and Apparatus for Light Emission Utilizing an OLED with a Microcavity
US7750564B2 (en) * 2006-12-04 2010-07-06 Samsung Mobile Display Co., Ltd. High efficiency organic light emitting device
US20080129191A1 (en) * 2006-12-04 2008-06-05 Sung-Hun Lee High efficiency organic light emitting device
US8304796B2 (en) 2007-11-14 2012-11-06 Canon Kabushiki Kaisha Light-emitting apparatus
US20100219427A1 (en) * 2007-11-14 2010-09-02 Canon Kabushiki Kaisha Light-emitting apparatus
US8018149B2 (en) * 2008-01-11 2011-09-13 Seiko Epson Corporation Light-emitting apparatus including optical resonance structure and electronic apparatus
US20090179563A1 (en) * 2008-01-11 2009-07-16 Seiko Epson Corporation Light-emitting apparatus and electronic apparatus
US20110079772A1 (en) * 2008-01-18 2011-04-07 Astron Fiamm Safety Organic light-emitting diode with microcavity including doped organic layers and fabrication process thereof
US8969853B2 (en) 2008-01-18 2015-03-03 Astron Fiamm Safety Sarl Organic light-emitting diode with microcavity including doped organic layers and fabrication process thereof
US20100059780A1 (en) * 2008-09-10 2010-03-11 Tpo Displays Corp. System for displaying images
US8598788B2 (en) * 2008-09-10 2013-12-03 Chimei Innolux Corporation System for displaying images
CN102217421A (en) * 2008-12-26 2011-10-12 松下电器产业株式会社 Organic el element, organic el display device, and method for manufacturing organic el element
US8912532B2 (en) 2009-04-07 2014-12-16 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Patterning the emission colour in top-emissive OLEDs
US8541941B2 (en) 2009-06-11 2013-09-24 Pioneer Corporation Light emitting element
US8339033B2 (en) 2009-06-11 2012-12-25 Pioneer Corporation Light emitting element and display device
US9185772B2 (en) 2009-07-28 2015-11-10 Pioneer Corporation Light-emitting element and display device
CN102201543B (en) * 2010-03-26 2015-09-16 Udc爱尔兰有限责任公司 Organic electric-field light-emitting element and use its organic electric field luminescent display
CN102201543A (en) * 2010-03-26 2011-09-28 富士胶片株式会社 Organic electric field luminous element and organic electric field luminescent display using the same
WO2014083693A1 (en) * 2012-11-30 2014-06-05 パイオニア株式会社 Light emitting device
US11557747B2 (en) 2018-11-12 2023-01-17 Wuhan Tianma Micro-Electronics Co., Ltd. Display device
CN112242493A (en) * 2019-07-17 2021-01-19 密西根大学董事会 Organic light emitting device
EP3772758A3 (en) * 2019-07-17 2021-04-21 The Regents of The University of Michigan Organic light emitting device
US11825687B2 (en) 2019-07-17 2023-11-21 The Regents Of The University Of Michigan Organic light emitting device

Also Published As

Publication number Publication date
JPH11288786A (en) 1999-10-19

Similar Documents

Publication Publication Date Title
US6406801B1 (en) Optical resonator type organic electroluminescent element
US6469437B1 (en) Highly transparent organic light emitting device employing a non-metallic cathode
US6831406B1 (en) Electroluminescent device having a very thin emission layer
EP0849979A2 (en) Organic electroluminescent color display
JP2005044778A (en) Electroluminescent device
JPH0765958A (en) Organic el element
JPH0963771A (en) Organic thin film luminescent element
KR20010107695A (en) Reduction of ambient-light-reflection in organic light-emitting devices
JPH11224783A (en) Organic electroluminescence element
JP2000268980A (en) Organic electroluminescent element
KR100621442B1 (en) Organic electroluminescent device, method for manufacturing the organic electroluminescent device, and organic electroluminescent display apparatus
US7061175B2 (en) Efficiency transparent cathode
JP3852518B2 (en) Organic electroluminescence device
JP4644938B2 (en) Organic electroluminescence device
JP3820752B2 (en) Organic electroluminescence device
US20060220535A1 (en) Organic electroluminescent element and display device
JP3852517B2 (en) Organic electroluminescence device
JP3555736B2 (en) Organic electroluminescent device
KR100572654B1 (en) Organic Electroluminescent Device
JP2002260858A (en) Light-emitting element and its manufacturing method
JP4104339B2 (en) LIGHT EMITTING ELEMENT, MANUFACTURING METHOD THEREOF, AND DISPLAY DEVICE
KR100581639B1 (en) Organic Electroluminescent Device
JP4748835B2 (en) lighting equipment
US6727660B1 (en) Organic electroluminescent devices and method for improving energy efficiency and optical stability thereof
JP2003272853A (en) Light emitting element and driving method of the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:TOKITO, SHIZUO;NODA, KOJI;FUJIKAWA, HISAYOSHI;AND OTHERS;REEL/FRAME:009867/0796

Effective date: 19990127

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362